Black dye mixtures of fiber-reactive azo dyes and use thereof for dyeing hydroxy- and/or carboxamido-containing fiber material

ABSTRACT

The disclosed black dye mixtures contain 50 to 95% by weight of one or more disazo dyes of the formula (1) and 5 to 50% by weight of one or more monoazo dyes of the formula (2) ##STR1## where R 1 , R 2 , R 3 , R 4 , R 5  and R 6 , identical to or different from each other, are each hydrogen, methyl, ethyl, methoxy, ethoxy, sulfo or carboxy, 
     Y is in each instance independently of the others vinyl, β-chloroethyl, βthiosulfatoethyl or β-sulfatoethyl, and 
     M is hydrogen or an alkali metal.

DESCRIPTION

Black dye mixtures of fiber-reactive azo dyes and use thereof for dyeinghydroxy- and/or carboxamido-containing fiber material

The present invention relates to the field of fiber-reactive dyes.

The present invention provides dye mixtures comprising one or more, suchas 1, 2 or 3, disazo dyes conforming to the formula (1), and one ormore, such as 1, 2 or 3, monoazo dyes conforming to the formula (2)##STR2## in an amount of from 50 to 95% by weight in respect of thedisazo dye(s) of the formula (1) and from 5 to 50% by weight in respectof the dye(s) of the formula (2).

The meanings of the symbols in the formulae (1) and (2) are as follows:

R¹ is hydrogen, methyl, ethyl, methoxy, ethoxy, sulfo or carboxy,preferably methoxy and hydrogen and in particular hydrogen,

R² is hydrogen, methyl, ethyl, methoxy, ethoxy, sulfo or carboxy,preferably hydrogen,

R³ is hydrogen, methyl, ethyl, methoxy, ethoxy, sulfo or carboxy,preferably methoxy and hydrogen and in particular hydrogen,

R⁴ is hydrogen, methyl, ethyl, methoxy, ethoxy, sulfo or carboxy,preferably hydrogen,

R⁵ is hydrogen, methyl, ethyl, methoxy, ethoxy, sulfo or carboxy,preferably methoxy and hydrogen and in particular hydrogen,

R⁶ is hydrogen, methyl, ethyl, methoxy, ethoxy, sulfo or carboxy,preferably hydrogen,

Y is in each instance independently of the others vinyl, β-chloroethyl,β-thiosulfatoethyl or β-sulfatoethyl,

M is hydrogen or an alkali metal, such as lithium, sodium and potassium;

the groups --SO₂ --Y are preferably bonded to the benzene ring meta orpara to the azo group.

The individual symbols appearing in the formulae (1) and (2) can haveidentical or different meanings within their definition.

The mixtures may additionally comprise a yellow or red shading dye in anamount of up to 10% by weight, preferably up to 5% by weight. Known dyesof this type are for example monoazo dyes conforming to the formulae(a), (b), (c) and (d) ##STR3## where D is3-(β-sulfatoethylsulfonyl)phenyl, 4-(β-sulfatoethylsulfonyl)phenyl,3-vinylsulfonylphenyl, 4-vinylsulfonylphenyl,2-methoxy-5-(β-sulfatoethylsulfonyl)phenyl or2-methoxy-5-vinylsulfonylphenyl,

M is as defined above,

R¹⁰ is acetyl, benzoyl, 4,6-dicyanamido-1,3,5-triazin-2-yl,4-cyanamido-6-(sulfophenylamino)-1,3,5-triazin-2-yl,4-(N-morpholino)-6-(sulfophenylamino)-1,3,5-triazin-2-yl or4-(N-morpholino)-6-(sulfophenylamino)-1,3,5-triazin-2-yl, substituted inthe benzene ring by methyl or methoxy,

R¹¹ is acetyl, carbamoyl, 4,6-dicyanamido-1,3,5-triazin-2-yl,4-cyanamido-6-(sulfophenylamino)-1,3,5-triazin-2-yl,4-(N-morpholino)-6-(sulfophenylamino)-1,3,5-triazin-2-yl or4-(N-morpholino)-6-(sulfophenylamino)-1,3,5-triazin-2-yl, substituted inthe benzene ring by methyl or methoxy,

R¹² is methyl or carboxy,

R¹³ is sulfo, β-chloroethylsulfonyl or β-sulfatoethylsulfonyl,

R¹⁴ is hydrogen or methyl,

R¹⁵ is hydrogen, cyano, carbamoyl, carboxy or sulfomethyl,

R¹⁶ is methyl, ethyl or β-sulfoethyl.

The dyes of the formulae (1) and (2) are well known from the literature,for example the disazo dyes of the formula (1) for example from U.S.Pat. No. 2,657,205 and from Japanese Patent Application PublicationSho-58-160 362 and also from U.S. Pat. No. 4,257,770 and the referencescited therein. Monoazo dyes of the formula (2) are described in U.S.Pat. No. 5,093,483.

The mixtures of the dyes of the formulae (1) and (2) preferably comprisethe disazo dye(s) of the formula (1) in an amount of from 60 to 80% byweight and the monoazo dye(s) of the formula (2) in an amount of from 20to 40% by weight.

A sulfo group is a group of the formula --SO₃ M, a carboxyl group is agroup of the formula --COOM, a sulfato group is a group of the formula--OSO₃ M, and a thiosulfato group is a group of the formula --S--SO₃ M.

The dyes of formula (1), and also the dyes of formula (2), in particularif they have the same chromophore, can have, within the meaning of Y,structurally different fiber-reactive groups --SO₂ --Y. In particular,the dye mixture can contain dyes of the same chromophore conforming tothe formula (1) and/or dyes of the same chromophore conforming to theformula (2) in which the fiber-reactive groups --SO₂ --Y are partlyvinylsulfonyl groups and partly β-chloroethylsulfonyl orβ-thiosulfatoethylsulfonyl or preferably β-sulfatoethylsulfonyl groups.If the dye mixtures contain the respective dye components in the form ofa vinylsulfonyl dye, the proportion of the respective vinylsulfonyl dyeto the respective β-chloro- or β-thiosulfato- or β-sulfatoethylsulfonyldye will be up to about 30 mol-%, based on the respective dyechromophore.

Preference is here given to dye mixtures in which the proportion ofvinylsulfonyl dye to β-sulfatoethylsulfonyl dye is in terms of the molarratio between 5:95 and 30:70.

Preference is further given to dye mixtures of one or more disazo dyesconforming to the formula (10) and one or more monoazo dyes conformingto the formula (11) ##STR4## where M is as defined above and D¹, D² andD³ are each independently of the others 3-vinylsulfonylphenyl,4-vinylsulfonylphenyl, 3-(β-sulfatoethylsulfonyl)phenyl or4-(β-sulfatoethylsulfonyl)phenyl, and if vinylsulfonyl as well asβ-sulfatoethylsulfonyl groups are present in the dye mixtures the molarratio between the vinylsulfonyl portions and the β-sulfatoethylsulfonylportions is in a molar ratio between 5:95 and 30:70.

Preference is further given to dye mixtures of one or more dyes of theformula (10) and one or more dyes of the formula (11) in which D¹ and D²are both independently of the other 3-(β-sulfatoethylsulfonyl)phenyl,4-(β-sulfatoethylsufonyl)phenyl, 3-vinylsulfonylphenyl or4-vinylsulfonylphenyl and D³ is2-methoxy-5-(β-sulfatoethylsulfonyl)phenyl or2-methoxy-5-vinylsulfonylpheny, and if

vinylsulfonyl as well as β-sulfatoethylsulfonyl groups are present inthe dye mixtures the molar ratio between the vinylsulfonyl portions andthe β-sulfatoethylsulfonyl portions is in a molar ratio between 5:95 and30:70.

The dye mixtures of the invention can be prepared in solid or in liquid(dissolved) form. In solid form they generally contain the electrolytesalts customary in the case of water-soluble and in particularfiber-reactive dyes, such as sodium chloride, potassium chloride andsodium sulfate, and also the assistants customary in commercial dyes,such as buffer substances capable of establishing a pH in aqueoussolution between 3 and 7, such as sodium acetate, sodium borate, sodiumbicarbonate, sodium dihydrogenphosphate and disodium hydrogenphosphate,small amounts of siccatives or, if they are present in liquid, aqueoussolution (including the presence of thickeners of the type customary inprint pastes), substances which ensure the permanence of thesepreparations, for example mold preventatives.

In general, the dye mixtures will take the form of dye powderscontaining from 10 to 80% by weight, based on the dye powder orpreparation, of a strength-standardizing colorless diluent electrolytesalt. These dye powders may in addition contain the abovementionedbuffer substances in a total amount of up to 5%, based on the dyepowder. If the dye mixtures of the invention are present in aqueoussolution, the total dye content of these aqueous solutions is up toabout 50% by weight, for example between 5 and 50% by weight, theelectrolyte salt content of these aqueous solutions preferably beingbelow 10% by weight, based on the aqueous solution; the aqueoussolutions (liquid preparations) can in general contain theabovementioned buffer substances in an amount of up to 5% by weight,preferably up to 2% by weight.

The dye mixtures of the invention can be obtained in a conventionalmanner, for instance by mechanically mixing the individual dyes in therequired proportions or by synthesis by means of the customarydiazotization and coupling reactions using appropriate mixtures of thediazo and coupling components in a manner familiar to those skilled inthe art and the necessary proportions. One option is for example toprepare aqueous solutions of the two coupling components1-amino-8-naphthol-3,6-disulfonic acid and2-hydroxynaphthalene-6-carboxylic acid and, as diazo components, of theaniline compounds of the formulae (3a), (3b) and/or (4) ##STR5## whereR¹, R², R³, R⁴, R⁵, R⁶ and Y are each as defined above, in theappropriate proportions, diazotizing these aniline compounds in aconventional manner in a strongly acid medium and then carrying out thecoupling reaction of 1-amino-8-naphthol-3,6-disulfonic acid with one ofthese diazo components at a pH below 1.5. The second coupling reactionwith the monoazo dye product to form the disazo dye is carried out witha further diazo component at a pH between 3 and 6. Then, by addition ofthe aqueous solution of 2-hydroxynaphthalene-6-carboxylic acid and of afurther diazo component, the coupling reaction to form the monoazo dyeconforming to the formula (2) is carried out at a pH between 3 and 6.The dye mixture thus obtained can be isolated from the solution in aconventional manner, for example by salting out with an electrolytesalt, such as sodium chloride, potassium chloride or lithium chloride,or by spray drying.

Dye mixtures in which the dye chromophores contain for example not onlya β-chloroethylsulfonyl or β-thiosulfatoethylsulfonyl orβ-sulfatoethylsulfonyl group but also proportions with vinylsulfonylgroups cannot only be prepared by the abovementioned method but alsousing appropriate vinylsulfonyl starting anilines by reacting the dyemixture in which Y is a β-chloroethyl or β-thiosulfatoethylβ-sulfatoethyl radical with an amount of alkali required for only partof these groups and converting part of said β-substituted ethylsulfonylgroups into vinylsulfonyl groups. This measure is carried out bygenerally known methods of converting β-substituted ethylsulfonyl groupsinto the vinylsulfonyl group.

The novel mixtures of the dyes of the formulae (1) and (2) dye hydroxy-and/or carboxamido-containing fiber materials by the application andfixing methods numerously described in the art for fiber-reactive dyesin deep black shades with a good color buildup and good washoff inrespect of unfixed dye portions. Moreover, the dyeings obtained arereadily dischargeable.

The present invention therefore also provides for the use of the noveldye mixtures for dyeing (including printing) hydroxy- and/orcarboxamido-containing fiber materials and processes for dyeing suchfiber materials using a dye mixture according to the invention byapplying the dye mixture to the substrate in dissolved form and fixingthe dyes on the fiber by the action of an alkali or by heating or both.

Hydroxy-containing materials are natural or synthetic hydroxy-containingmaterials, for example cellulose fiber materials, including in the formof paper, or their regenerated products and polyvinyl alcohols.

Cellulose fiber materials are preferably cotton but can also be othervegetable fibers, such as linen, hemp, jute and ramie fibers;regenerated cellulose fibers are for example staple viscose and filamentviscose.

Carboxamido-containing materials are for example synthetic and naturalpolyamides and polyurethanes, in particular in the form of fibers, forexample wool and other animal hairs, silk, leather, nylon-6.6, nylon-6,nylon-11 and nylon-4.

Application of the dye mixtures of the invention is by generally knownprocesses for dyeing and printing fiber materials by the knownapplication techniques for fiber-reactive dyes. Since the dyes of thedye mixtures according to the invention are highly compatible with oneanother, the dye mixtures of the invention are also advantageouslyuseful in exhaust dyeing processes. Applied in this way for example tocellulose fibers from a long liquor at temperatures between 40° and 105°C., optionally at temperatures up to 130° C. under superatmosphericpressure, and optionally in the presence of customary dyeing assistantswith the use of acid-binding agents and optionally neutral salts, suchas sodium chloride or sodium sulfate, they produce dyeings in very goodcolor yields with excellent color buildup and consistent shade. Onepossible procedure is to introduce the material into the warm bath,gradually heat the bath to the desired dyeing temperature, and completethe dyeing process at that temperature. The neutral salts which speed upthe exhaustion of the dyes can also if desired not be added to the bathuntil the actual dyeing temperature has been reached.

Similarly, the conventional printing processes for cellulosefibers--which can either be carried out in single-phase, for example byprinting with a print paste containing sodium bicarbonate or some otheracid-binding agent and the colorant, and subsequent steaming at from100° to 103° C., or in two phases, for example by printing with aneutral or weakly acid print paste containing the colorant andsubsequent fixation either by passing the printed material through a hotelectrolyte-containing alkaline bath or by overpadding with an alkalineelectrolyte-containing padding liquor and subsequent batching of thistreated material or subsequent steaming or subsequent treatment with dryheat--produce strong prints with well defined contours and a clear whiteground. Changing fixing conditions has only little effect on the outcomeof the prints. Not only in dyeing but also in printing the degrees offixation obtained with the dye mixtures of the invention are very high.The hot air used in dry heat fixing by the customary thermofix processeshas a temperature of from 120° to 200° C. In addition to the customarysteam at from 101° to 103° C. it is also possible to use superheatedsteam and high pressure steam at up to 160° C.

Acid-binding agents responsible for fixing the dyes to the cellulosefibers are for example water-soluble basic salts of alkali metals and ofalkaline earth metals of inorganic or organic acids, and compounds whichrelease alkali when hot. Of particular suitability are the alkali metalhydroxides and alkali metal salts of weak to medium inorganic or organicacids, the preferred alkali metal compounds being the sodium andpotassium compounds. These acid-binding agents are for example sodiumhydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate,potassium carbonate, sodium formate, sodium dihydrogenphosphate anddisodium hydrogenphosphate.

Treating the dyes of the dye mixtures according to the invention withthe acid-binding agents with or without heating bonds the dyeschemically to the cellulose fiber; especially the dyeings on cellulose,after they have been given the usual aftertreatment of rinsing to removeunfixed dye portions, show excellent wet fastness properties, inparticular since the unfixed dye portions are readily washed off becauseof their good cold water solubility.

The dyeings of polyurethane and polyamide fibers are customarily carriedout from an acid medium. The dyebath may contain for example acetic acidand/or ammonium sulfate and/or acetic acid and ammoniumacetate or sodiumacetate to bring it to the desired pH. To obtain a dyeing of acceptablelevelness it is advisable to add customary leveling assistants, forexample based on a reaction product of cyanuric chloride with threetimes the molar amount of an aminobenzenesulfonic acid oraminonaphthalenesulfonic acid or based on a reaction product of forexample stearylamine with ethylene oxide. In general the material to bedyed is introduced into the bath at a temperature of about 40° C. andagitated therein for some time, the dyebath is then adjusted to thedesired weakly acid, preferably weakly acetic acid, pH, and the actualdyeing is carried out at a temperature between 60° and 98° C. However,the dyeings can also be carried out at the boil or at temperatures of upto 120° C. (under superatmospheric pressure).

The Examples which follow illustrate the invention. Parts andpercentages are by weight, unless otherwise stated. The parts by weightbear the same relation to parts by volume as the kilogram to the liter.

EXAMPLE 1

200 parts of an electrolyte-containing dye powder which contains thenavy-dyeing disazo dye of the formula (A) ##STR6## in a proportion of50% are mechanically mixed with 75 parts of an electrolyte-containingdye powder which contains the golden yellow-dyeing monoazo dye of theformula (B) ##STR7## in a proportion of 70%. The resulting dye mixtureaccording to the invention, when employed according to the applicationand fixing methods customary in the art for fiber-reactive dyes,produces for example on cellulose fiber materials dyeings and prints indeep black shades.

EXAMPLE 2

A dye mixture according to the invention is prepared by adjusting asuspension of 288 parts of 4-(β-sulfatoethylsulfonyl)aniline in 250parts of water to a pH of from 4.5 to 5 with about 59 parts of sodiumcarbonate, diazotizing the aniline compound with 143 parts by volume ofa 38% strength aqueous sodium nitrite solution following addition of 234parts by volume of a 30% strength aqueous hydrochloric acid and 400parts of ice, then adding 112 parts of 1-amino-8-naphthol-3,6-disulfonicacid and carrying the first coupling reaction out at a pH between 1 and1.3 and at a temperature of below 20° C. (the pH is maintained withabout 60 parts of sodium bicarbonate), then adding 57 parts of2-hydroxynaphthalene-6-carboxylic acid, adjusting with sodium carbonateto a pH of from 5 to 6, and carrying out the coupling reaction at 20° C.and within that pH range.

The result is a black dye solution containing the dyes of the formulae(A) and (B) mentioned in Example 1 in the ratio 68.7%:31.3%.

This dye solution can be adjusted to pH 4.5 by adding 5 parts of asodium phosphate buffer. By further diluting with water or byevaporating the solution, this liquid dye mixture can then bestandardized to the desired strength for a liquid preparation, which ina conventional manner is either used directly as a dyebath or dyeingliquor, optionally following addition of the appropriate amount of analkaline agent, or used for preparing a dyebath or dyeing liquor. Thedye mixture gives deep black dyeings.

EXAMPLE 2a

The method described in Example 2 can be used to prepare a similar dyemixture by varying the amount used of the starting compounds, forexample by using the 4-(β-sulfatoethylsulfonyl)aniline in an amount of280 parts, the 1-amino-8-naphthol-3,6-disulfonic acid in an amount of102 parts and the 2-hydroxynaphthalene-6-carboxylic acid in an amount of68 parts. The result obtained is a dye mixture in which the dyes of theformulae (A) and (B) are present in the ratio of about 62.7% :37.3%. Thedye mixture can be isolated from the synthesis solution, for example byspray drying, or else be used directly for dyeing as described inExample 2 in the dissolved form of a liquid preparation. Employedaccording to the application and fixing methods customary in the art itlikewise produces, for example on cellulose fiber materials, deep blackdyeings.

EXAMPLE 3

To prepare a dye mixture in which some of the dyes have aβ-sulfatoethylsulfonyl group while the rest has a vinylsulfonyl group,the solution of the novel dye mixture prepared in Example 2 is used asthe starting point. 25% by volume of this solution is separated off,adjusted with sodium carbonate to pH 8 and subsequently stirred at 20°C. for a further 15 minutes, in the course of which theβ-sulfatoethylsulfonyl groups are transformed into vinylsulfonyl groups.Thereafter sulfuric acid is used to set a pH of 4.5 and this solution ofthe vinylsulfonyl dye mixture is added to the original solution of theβ-sulfatoethylsulfonyl dye mixture. The result is an aqueous solution ofdyes conforming to the formulae (A-1) and (B-1) ##STR8## where Y is 25%vinyl and 75% β-sulfatoethyl.

Inorganic salts such as sodium sulfate, which have been additionallybrought by this measure into the aqueous dye solutions, can to someextent be isolated by cooling the solution down to 0° C. and filteredoff.

The filtrate is adjusted with 5 parts of sodium phosphate buffer to a pHof 4.5. By adding or evaporating water, this aqueous solution can beadjusted to the strength desired for a liquid preparation and be usedfor dyeing in the manner indicated in Example 2. The application andfixing methods customary in the art for fiber-reactive dyes produce deepblack dyeings and prints.

EXAMPLE 4

A dye mixture according to the invention is prepared by adjusting asuspension of 118 parts of 4-(β-sulfatoethylsulfonyl)aniline in 100parts of water to a pH of from 4.5 to 5 with 20 parts of sodiumcarbonate, subsequently stirring for some time and then diazotizing with59 parts by volume of a 38% strength sodium nitrite solution followingaddition of 100 parts by volume of a 31% strength aqueous hydrochloricacid and 200 parts of ice.

After the diazotization reaction has ended, 134 parts of1-amino-8-naphthol-3,6-disulfonic acid are added, the first couplingreaction is carried out at a temperature below 20° C. while maintaininga pH of from 1 to 1.3, and the resulting monoazo compound is thenisolated by salting out with sodium chloride.

In a separate batch, a solution of 261 parts of2-methoxy-5-(β-sulfatoethylsulfonyl)aniline and 300 parts of water isadmixed with 190 parts by volume of a 31% strength aqueous hydrochloricacid and 300 parts of ice and diazotized by means of 117.5 parts byvolume of a 38% strength aqueous sodium nitrite solution. To thisdiazonium salt solution are then added the monoazo compound obtained asdirected above and 79 parts of 2-hydroxynaphthalene-6-carboxylic acid,and the coupling reaction is carried out at a temperature of about 20°C. while maintaining a pH between 5 and 6.

The resulting solution of a novel dye mixture of the dye of the formula(A) and of the dye (C) ##STR9## can be put to dyeing use in aconventional manner either directly following isolation of the dyemixture from the synthesis solution by spray drying or by salting outwith sodium chloride or directly in the dissolved form. Again, customaryapplication and fixing methods for fiber-reactive dyes produce, forexample on cellulose fiber materials, dyeings of a deep black shade.

EXAMPLE 5

A dye mixture according to the invention can be prepared by preparingthe disazo dye of the formula (A) and the monoazo dye (D) ##STR10## inseparate batches in a conventional manner and mixing the two dyesolutions in appropriate proportions to form the aqueous solution of adye mixture according to the invention.

For instance, the disazo dye of the formula (A) can be prepared bydiazotizing and coupling the diazonium salt of 292 parts of4-(β-sulfatoethylsulfonyl)aniline with 159 parts of1-amino-8-naphthol-3,6-disulfonic acid and the dye of the formula (D) bydiazotizing 162.6 parts of2-methoxy-5-methyl-4-(β-sulfatoethylsulfonyl)aniline and coupling with94 parts of 2-hydroxynaphthalene-6-carboxylic acid and mixing the tworesulting dye solutions. This dye mixture too, employed by theapplication and fixing methods customary in the art for fiber-reactivedyes, produces for example on cotton deep black dyeings.

EXAMPLE 6

80 parts of an electrolyte-containing dye powder which contains theorange-dyeing monoazo dye of the abovementioned formula (C) in aproportion of 70%, 200 parts of an electrolyte-containing dye powderwhich contains the navy-dyeing disazo dye of the formula (A) in aproportion of 50% and--for the purpose of shading--20 parts of anelectrolyte-containing dye powder which contains the yellow-dyeingmonoazo dye of the formula (E) ##STR11## in a proportion of 50% aremechanically mixed with one another. The dye mixture according to theinvention, employed according to the application and fixing methodscustomary in the art for fiber-reactive dyes, produces for example oncellulose fiber materials dyeings and prints in deep black shades.

EXAMPLE 7

100 parts of an electrolyte-containing dye powder which contains thegolden yellow-dyeing monoazo dye of the formula (F) ##STR12## in aproportion of 60%, 200 parts of an electrolyte-containing dye powderwhich contains the navy-dyeing disazo dye of the formula (A) in aproportion of 50% and--for the purpose of shading--20 parts of anelectrolyte-containing dye powder which contains the red-dyeing monoazodye of the formula (G) ##STR13## in a proportion of 50% are mechanicallymixed with one another. The dye mixture according to the invention,employed by the application and fixing methods customary forfiber-reactive dyes, produces for example on cellulose fiber materialsdyeings and prints in deep black shades.

EXAMPLE 8

Example 2a is repeated with the following starting compounds andamounts:

290 parts of 4-(β-sulfatoethylsulfonyl)aniline, 102 parts of1-amino-8-naphthol-3,6-disulfonic acid, 64 parts of2-hydroxynaphthalene-6-carboxylic acid and 17 parts of1-benzoylamino-8-naphthol-3,6-disulfonic acid.

The result is a dye mixture which dyes cellulose fiber materials in adeep black shade.

EXAMPLE 9

72.4 parts of an electrolyte-containing dye powder which contains thenavy-dyeing disazo dye of the formula (A) in a proportion of 50% aremechanically mixed with 27.54 parts of an electrolyte-containing dyepowder which contains the golden yellow-dyeing monoazo dye of theformula (B) in a proportion of 50%. The resulting dye mixture accordingto the invention, in which the dyes (A) and (B) are present in a ratioof 2.63:1, produces for example on cellulose fiber materials dyeings andprints in deep black shades when employed by the application and fixingmethods customary in the art for fiber-reactive dyes. Not only is thecolor buildup good, the unfixed dye portions are readily washed off andthe dyeing is dischargeable.

EXAMPLES 10 TO 40

The table examples which follow describe further novel dye mixtures ofthe dyes conforming to the formulae (10) and (11) ##STR14## in terms ofthe components of these dyes (M has one of the abovementioned meanings).In the mixing ratio according to the invention and when employedaccording to the application and fixing methods customary in the art forfiber-reactive dyes these dye mixtures to produce for example oncellulose fiber materials deep black dyeings.

    ______________________________________                                        Dye mixture of                                                                Disazo dye (10)   Monoazo dye (11)                                            Ex.  Radical D.sup.1                                                                           Radical D.sup.2                                                                             Radical D.sup.3                                ______________________________________                                        10   ditto       2-carboxy-4-(β-                                                                        ditto                                                           sulfatoethylsul-                                                              fonyl)phenyl                                                 11   4-(β-  2-methoxy-5-methyl-                                                                         4-(β-                                          sulfatoethyl-                                                                             4-(β-    sulfatoethylful-                                    sulfonyl)-2,5-                                                                            sulfatoethylsul-                                                                            fonyl)-2,5-di-                                      disulfophenyl                                                                             fonyl)phenyl  sulfophenyl                                    12   2,5-dimethoxy-4-                                                                          4-(β-    2,5-dimethoxy-4-                                    (β-    sulfatoethylsul-                                                                            (β-sulfato-                                    sulfatoethylsul-                                                                          fonyl)phenyl  ethylsul-                                           fonyl)phenyl              fonyl)phenyl                                   13   4-(β-  2-methoxy-5-methyl-                                                                         4-(β-                                          sulfatoethylsul-                                                                          4-(β-    sulfatoethylsul-                                    fonyl)phenyl                                                                              sulfatoethylsul-                                                                            fonyl)phenyl                                                    fonyl)phenyl                                                 14   4-(β-  2,5-dimethoxy-4-                                                                            4-(β-                                          sulfatoethylsul-                                                                          (β-      sulfatoethylsul-                                    fonyl)phenyl                                                                              sulfatoethylsul-                                                                            fonyl)phenyl                                                    fonyl)phenyl                                                 15   2-methoxy-5-                                                                              4-(β-    2-methoxy-5-meth                                    methyl-4-(β-                                                                         sulfatoethylsul-                                                                            yl-4-(β-                                       sulfatoethylsul-                                                                          fonyl)phenyl  sulfatoethylsul-                                    fonyl)phenyl              fonyl)phenyl                                   16   4-(β-  2-sulfo-5-(β-                                                                          4-(β-                                          sulfatoethylsul-                                                                          sulfatoethylsul-                                                                            sulfatoethylsul-                                    fonyl)phenyl                                                                              fonyl)phenyl  fonyl)phenyl                                   17   2-sulfo-5-(β-                                                                        4-(β-    2-sulfo-5-(β-                                  sulfatoethylsul-                                                                          sulfatoethylsul-                                                                            sulfatoethylsul-                                    fonyl)phenyl                                                                              fonyl)phenyl  fonyl)phenyl                                   18   2,5-dimethoxy-4-                                                                          2,5-dimethoxy-4-(β-                                                                    4-(β-                                          (β-    sulfatoethylsul-                                                                            sulfatoethylsul-                                    sulfatoethylsul-                                                                          fonyl)phenyl  fonyl)phenyl                                        fonyl)phenyl                                                             19   4-(β-  4-(β-    2-methoxy-5-(β-                                sulfatoethylsul-                                                                          sulfatoethylsul-                                                                            sulfatoethylsul-                                    fonyl)phenyl                                                                              fonyl)phenyl  fonyl)phenyl                                   20   2-carboxy-4-(β-                                                                      2-carboxy-4-(β-                                                                        2-methoxy-5-meth-                                   sulfatoethylsul-                                                                          sulfatoethylsul-                                                                            yl-4-(β-                                       fonyl)phenyl                                                                              fonyl)phenyl  sulfatoethylsul-                                                              fonyl)phenyl                                   21   4-(β-  4-(β-    2-carboxy-4-(β-                                sulfatoethylsul-                                                                          sulfatoethylsul-                                                                            sulfatoethylsul-                                    fonyl)phenyl                                                                              fonyl)phenyl  fonyl)phenyl                                   22   2-carboxy-4-(β-                                                                      2-carboxy-4-(β-                                                                        4-(β-sulfato-                                  sulfatoethylsul-                                                                          sulfatoethylsul-                                                                            ethylsulfonyl)                                      fonyl)phenyl                                                                              fonyl)phenyl  phenyl                                         23   2-methoxy-5-                                                                              2-methoxy-5-  3-(β-sulfato-                                  methyl-4-(β-                                                                         methyl-4-(β-                                                                           ethylsulfonyl-                                      sulfatoethylsul-                                                                          sulfatoethylsul-                                                                            phenyl                                              fonyl)phenyl                                                                              fonyl)phenyl                                                 24   2-methoxy-5-(β-                                                                      2-methoxy-5-(β-                                                                        2-methoxy-5-                                        sulfatoethylsul-                                                                          sulfatoethylsul-                                                                            methyl-4-(β-                                   fonyl)phenyl                                                                              fonyl)phenyl  sulfatosulfonyl)-                                                             phenyl                                         25   2-sulfo-5-(β-                                                                        2-sulfo-5-(β-                                                                          4-(β-                                          sulfatoethylsul-                                                                          sulfatoethylsul-                                                                            sulfatoethylsul-                                    fonyl)phenyl                                                                              fonyl)phenyl  fonyl)phenyl                                   26   4-(β-  4-(β-    2-sulfo-5-(β-                                  sulfatoethylsul-                                                                          sulfatoethylsul-                                                                            sulfatoethylsul-                                    fonyl)phenyl                                                                              fonyl)phenyl  fonyl)phenyl                                   27   2-methoxy-5-                                                                              2-methoxy-5-  4-(β-                                          methyl-4-(β-                                                                         methyl-4-(β-                                                                           sulfatoethylsul-                                    sulfatoethylsul-                                                                          sulfatoethylsul-                                                                            fonyl)phenyl                                        fonyl)phenyl                                                                              fonyl)phenyl                                                 28   3-(β-  3-(β-    2-methoxy-5-                                        sulfatoethylsul-                                                                          sulfatoethylsul-                                                                            methyl-5-(β-                                   fonyl)phenyl                                                                              fonyl)phenyl  sulfatoethylsul-                                                              fonyl)phenyl                                   29   3-(β-  3-(β-    4-(β-                                          sulfatoethylsul-                                                                          sulfatoethylsul-                                                                            sulfatoethylsul-                                    fonyl)phenyl                                                                              fonyl)phenyl  fonyl)phenyl                                   30   2-methoxy-5-(β-                                                                      2-methoxy-5-(β-                                                                        3-(β-                                          sulfatoethylsul-                                                                          sulfatoethylsul-                                                                            sulfatoethylsul-                                    fonyl)phenyl                                                                              fonyl)phenyl  fonyl)phenyl                                   31   2-methoxy-5-(β-                                                                      2-methoxy-5-(β-                                                                        2-sulfo-5-(β-                                  sulfatoethylsul-                                                                          sulfatoethylsul-                                                                            sulfatoethylsul-                                    fonyl)phenyl                                                                              fonyl)phenyl  fonyl)phenyl                                   32   2-methoxy-5-(β-                                                                      2-methoxy-5-(β-                                                                        2-sulfo-4-(β-                                  sulfatoethylsul-                                                                          sulfatoethylsul-                                                                            sulfatoethylsul-                                    fonyl)phenyl                                                                              fonyl)phenyl  fonyl)phenyl                                   33   2-sulfo-5-(β-                                                                        2-sulfo-5-(β-                                                                          4-(β-                                          sulfatoethylsul-                                                                          sulfatoethylsul-                                                                            sulfatoethylsul-                                    fonyl)phenyl                                                                              fonyl)phenyl  fonyl)phenyl                                   34   2-sulfo-5-(β-                                                                        2-sulfo-5-(β-                                                                          3-(β-                                          sulfatoethylsul-                                                                          sulfatoethylsul-                                                                            sulfatoethylsul-                                    fonyl)phenyl                                                                              fonyl)phenyl  fonyl)phenyl                                   35   4-(β-  4-(β-    2-sulfo-5-(β-                                  sulfatoethylsul-                                                                          sulfatoethylsul-                                                                            sulfatoethylsul-                                    fonyl)phenyl                                                                              fonyl)phenyl  fonyl)phenyl                                   365  4-(β-  4-(β-    3-(β-                                          sulfatoethylsul-                                                                          sulfatoethylsul-                                                                            sulfatoethylsul-                                    fonyl)phenyl                                                                              fonyl)phenyl  fonyl)phenyl                                   37   2-methoxy-5-                                                                              2-methoxy-5-  4-(β-                                          methyl-4-(β-                                                                         methyl-4-(β-                                                                           sulfatoethylsul-                                    sulfatoethylsul-                                                                          sulfatoethylsul-                                                                            fonyl)phenyl                                        fonyl)phenyl                                                                              fonyl)phenyl                                                 38   2-methoxy-5-                                                                              2-methoxy-5-  2-sulfo-5-(β-                                  methyl-4-(β-                                                                         methyl-4-(β -                                                                          sulfatoethylsul-                                    sulfatoethylsul-                                                                          sulfatoethylsul-                                                                            fonyl)phenyl                                        fonyl)phenyl                                                                              fonyl)phenyl                                                 39   4-(β-  4-(β-    2,5-disulfo-4-(β-                              sulfatoethylsul-                                                                          sulfatoethylsul-                                                                            sulfatoethylsul-                                    fonyl)phenyl                                                                              fonyl)phenyl  fonyl)phenyl                                   40   4-(β-  2-carboxy-5-(β-                                                                        4-(β-                                          sulfatoethylsul-                                                                          sulfatoethylsul-                                                                            sulfatoethylsul-                                    fonyl)phenyl                                                                              fonyl)phenyl  fonyl)phenyl                                   ______________________________________                                    

What is claimed is:
 1. A dye mixture for preparing black dyeingscomprising one or more disazo dyes conforming to the formula ( 1) andone or more monoazo dyes conforming to the formula (2) ##STR15## whereR¹, R², R³, R⁴, R⁵ and R⁶, identical to or different from each other,are each hydrogen, methyl, ethyl, methoxy, ethoxy, sulfo or carboxy,Y isin each instance independently of the others vinyl, β-chloroethyl,β-thiosulfatoethyl or β-sulfatoethyl, and M is hydrogen or an alkalimetal, said mixture comprising an amount of from 50 to 95% by weight inrespect of the disazo dye(s) of the formula (1) and of from 5 to 50% byweight in respect of the dye(s) of the formula (2).
 2. The dye mixtureof claim 1, wherein the one or more disazo dyes conforming to theformula (1) account for from 60 to 80% by weight and the one or moremonoazo dyes conforming to the formula (2) account for from 40 to 20% byweight.
 3. The dye mixture of claim 1, wherein R¹, R³ and R⁵ are eachindependently of one another hydrogen or methoxy and R², R⁴ and R⁶ areeach hydrogen.
 4. The dye mixture of claim 1, wherein R¹, R², R³, R⁴, R⁵and R⁶ are each hydrogen.
 5. The dye mixture of claim 1, wherein Y is ineach instance independently of the others vinyl or β-sulfatoethyl. 6.The dye mixture of claim 1 comprising one or more disazo dyes conformingto the formula (10) and one or more monoazo dyes conforming to theformula (11) ##STR16## where D¹, D² and D³ are each independently of theothers 3-vinylsulfonylphenyl, 4-vinylsulfonylphenyl,3-(β-sulfatoethylsulfonyl)phenyl or 4-(β-sulfatoethylsulfonyl)phenyl andM is as defined in claim
 1. 7. The dye mixture of claim 1 comprising oneor more disazo dyes conforming to the formula (10) and one or moremonoazo dyes conforming to the formula (11) ##STR17## where D¹ and D²are both independently of the other 3-(β-sulfatoethylsulfonyl)phenyl,4-(β-sulfatoethylsulfonyl)phenyl, 3-vinylsulfonylphenyl or4-vinylsulfonylphenyl and D³ is2-methoxy-5-(β-sulfatoethylsulfonyl)phenyl or2-methoxy-5-vinylsulfonylphenyl and M is as defined in claim
 1. 8. Thedye mixture of claim 1, wherein the dyes are present as a mixture ofvinylsulfonyl and β-sulfatoethylsulfonyl dyes and the proportion ofvinylsulfonyl dye to β-sulfatoethylsulfonyl dye is in a molar ratiobetween 5:95 and 30:70.
 9. A method for dyeing a fiber materialcontaining hydroxy or carboxamide groups or both black, comprising thestep of dyeing the material black with a dye mixture of claim
 1. 10. Amethod for modifying the color of a dye which produces navy dyeings byformulating a dye mixture, said method comprising:selecting as thenavy-dyeing dye a compound of the formula (1) ##STR18## and modifyingthe coloristic properties of the navy-dyeing dye to obtain ablack-dyeing dye mixture by mixing 50 to 95% by weight, of the resultingdye mixture, of a said compound of the formula (1) with 5 to 50% byweight, of the resulting dye mixture, of a compound of the formula (2)##STR19## where R¹, R², R³, R⁴, R⁵ and R⁶, identical to or differentfrom each other, are each hydrogen, methyl, ethyl, methoxy, ethoxy,sulfo or carboxy, Y is in each instance independently of the othersvinyl, β-chloroethyl, β-thiosulfatoethyl or β-sulfatoethyl, and M ishydrogen or an alkali metal.